Tuning the hydrogen storage properties of MOF-650: A combined DFT and GCMC simulations study

Combined density functional theory and grand canonical monte Carlo (GCMC) calculations were performed to study the electronic structures and hydrogen adsorption properties of the Zn-based metal-organic framework MOF-650. The benzene azulenedicarboxylate linkers of MOF-650 were substituted by B atoms, N atoms, and boronic acid B(OH)₂ linkers, and the Zn atoms were substituted by Mg and Ca atoms. The calculated electronic densities of states (DOSs) of MOF-650 showed that introduction of B atoms reduces the band gap but damages the structure of MOF-650. Introduction of single N bonds cannot provide active electrons to attract H₂ molecules. Thus, substitutions of B and N into MOF-650 are not suggested. B(OH)₂ substitute in MOF-650 decreased its band gap, slightly improved its hydrogen storage ability and made H₂ molecules more intensively distributed besides organic linkers. GCMC calculations were carried out by estimating the H₂ storage amount of the pure and modified MOFs at 77 and 298 K and from 1 bar to 20 bar. B(OH)₂ linker and Mg/Ca co-doped MOF-650 showed increased H₂ adsorption by approximately 20 wt%. The adsorption of H₂ around different bonds showed the order N–C < C = C < B–C < C–O < B–O.     

Heterofullerene C48B12-impregnated MOF-5 and IRMOF-10 for hydrogen storage: A combined DFT and GCMC simulations study

The H₂ storage properties of isoreticular metal-organic framework materials (IRMOFs), MOF-5 and IRMOF-10, impregnated with different numbers and types of heterogeneous C₄₈B₁₂ molecules were investigated using density functional theory and grand canonical Monte Carlo (GCMC) calculations. The excess hydrogen adsorption isotherms of IRMOFs at 77 K within 20 bar indicate that suitable number and type of C₄₈B₁₂ molecules play a crucial role in improving the H₂ storage properties of IRMOFs. Among the studied pure and nC₄₈B₁₂ (n = 1, 2, 4, 8) in Ci symmetry impregnating into MOF-5, at 77 K under 6 bar, MOF-5-4C₄₈B₁₂ with a 3.5 wt% and 29.9 g/L hydrogen storage density, and at 77 K under 12 bar, the pure MOF-5 with a 4.9 wt% and 31.0 g/L hydrogen storage density has the best hydrogen storage properties. Whereas, among the studied pure and nC₄₈B₁₂ (n = 1, 2, 4, 8) in S6 symmetry impregnating into IRMOF-10, IRMOF-10-8C₄₈B₁₂ always shows the best hydrogen storage properties among the pure and C₄₈B₁₂-impregnated IRMOF-10 at 77 K within 20 bar. IRMOF-10-8C₄₈B₁₂ has a 6.0 wt% and 34.6 g/L hydrogen storage density at 77 K under 6 bar, and has a 7.1 wt% and 41.4 g/L hydrogen storage density at 77 K under 12 bar. The confinement effect of IRMOFs on C₄₈B₁₂ molecules, and steric hindrance effect of C₄₈B₁₂ molecules on IRMOFs mainly affects the H₂ uptake capacity by comparing the absolute H₂ molecules in individual IRMOFs units, C₄₈B₁₂ molecules, and IRMOFs-nC₄₈B₁₂ compounds. The absolute hydrogen adsorption profiles show that eight C₄₈B₁₂ molecules impregnating into MOF-5 can exert obvious steric effects for H₂ adsorption. The saturated gravimetric and volumetric H₂ densities of IRMOF-10-8C₄₈B₁₂ higher than those of MOF-5-8C₄₈B₁₂ due to with larger free volume.     

Molecular simulation of copper based metal-organic framework (Cu-MOF) for hydrogen adsorption

Metal organic framework (MOF) are widely used in adsorption and separation due to their porous nature, high surface area, structural diversity and lower crystal density. Due to their exceptional thermal and chemical stability, Cu-based MOF are considered excellent hydrogen storage materials in the world of MOFs. Efforts to assess the effectiveness of hydrogen storage in MOFs with molecular simulation and theoretical modeling are crucial in identifying the most promising materials before extensive experiments are undertaken. In the current work, hydrogen adsorption in four copper MOFs namely, MOF-199, MOF 399, PCN-6′, and PCN-20 has been analyzed. These MOFs have a similar secondary building unit (SBU) structure, i.e., twisted boracite (tbo) topology. The Grand Canonical Monte Carlo (GCMC) simulation was carried at room temperature (298 K) as well as at cryogenic temperature (77 K) and pressures ranging from 0 to 1 bar and 0–50 bar. These temperatures and pressure were selected to comply with the conditions set by department of energy (DOE) and to perform a comparative study on hydrogen adsorption at two different temperatures. The adsorption isotherm, isosteric heat, and the adsorption sites were analyzed in all the MOFs. The findings revealed that isosteric heat influenced hydrogen uptake at low pressures, while at high pressures, porosity and surface area affected hydrogen storage capacity. PCN-6′ is considered viable material at 298 K and 77 K due to its high hydrogen uptake.     

Hydrogen adsorption and kinetics in MIL-101(Cr) and hybrid activated carbon-MIL-101(Cr) materials

Since the last 15 years, porous solids such as Metal–Organic Frameworks (MOFs) have opened new perspectives for the development of adsorbents for hydrogen storage. Among all MOF materials, the chromium (III) terephthalate-based MIL-101(Cr) is a very stable one which exhibits a good uptake capacity of hydrogen (H₂). In this study, syntheses were carried out in soft conditions without hydrofluoric acid as usually reported in literature. Moreover, activated carbon (AC) was introduced in the preparation of the MOF-based adsorbents to create hybrid materials with large specific surface areas (AC-MOF). Hydrogen storage capacities were assessed at 77 K up to 100 bar, and the measurements of adsorption isotherms were performed using both volumetric and gravimetric methods. The experimental data were shown to be in good agreement. A maximal excess hydrogen uptake of 67.4 mol kg^?1 (13.5 wt.%) has been reached by the hybrid AC-MOF adsorbent at 77 K under 100 bar. The hydrogen storage capacity was so shown to be greatly enhanced by AC addition, as a maximal value of only 41.1 mol kg^?1(8.2 wt.%) was reported for the pristine MIL-101(Cr), under the same conditions. Finally, hydrogen adsorption kinetics were examined at 77 K using experimental transient adsorption curves obtained using volumetric method, and the Linear Driving Force (LDF) model was tested for their interpretation. According to this model, diffusion coefficients could be correctly estimated only in a very low pressure range. However, for high pressures, the quasi-equilibrium assumption is not valid at the initial adsorption times, making the LDF model no more applicable for accurate determination of the average effective diffusivities. To our knowledge we present the first measurement of the adsorption kinetics of hydrogen in a hybrid carbon MOF composite material. Moreover, the adsorption performances reported in this work are the best ones achieved until now by MIL-101(Cr) doping using carbonaceous materials.     

Synthesis and hydrogen adsorption properties of a new iron based porous metal-organic framework

A new metal-organic framework [Fe₃O(OOC-C₆H₄-COO)₃(H₂O)₃]Cl·(H₂O)_x was synthesized with a specific surface area of 2823 m²/g and a lattice parameter of 88.61 Å. Isostructural with MIL-101, this compound exhibits similar hydrogen adsorption properties, with maximum adsorption capacity of 5.1wt.% H at 77 K. The adsorption enthalpy of hydrogen for MIL-101 and ITIM-1 (MIL-101Fe) at zero coverage was calculated for a wide temperature range of 77 K ÷ 324 K, considering corrections for the variation of hydrogen gas entropy with the temperature. The resulted adsorption enthalpy is 9.4 kJ/mol for MIL-101, in excellent agreement with the value reported in literature from microcalorimetric measurements, and a value of 10.4 kJ/mol at zero coverage was obtained for ITIM-1 (MIL-101Fe).     

Hydrogen permeation and diffusion in densified MOF-5 pellets

The metal-organic framework Zn₄O (BDC)₃ (BDC = 1,4-bezene dicarboxlate), also known as MOF-5, has demonstrated considerable adsorption of hydrogen, up to 7 excess wt.% at 77 K. Consequently, it has attracted significant attention for vehicular hydrogen storage applications. To improve the volumetric hydrogen density and thermal conductivity of MOF-5, prior studies have examined the hydrogen storage capacities of dense MOF-5 pellets and the impact of thermally conductive additives such as expanded natural graphite (ENG). However, the performance of a storage system based on densified MOF-5 powders will also hinge upon the rate of hydrogen mass transport through the storage medium. In this study, we further characterize MOF-5 compacts by measuring their hydrogen transport properties as a function of pellet density (ρ = 0.3–0.5 g cm⁻³) and the presence/absence of ENG additions. More specifically, the Darcy permeability and diffusivity of hydrogen in pellets of neat MOF-5, and composite pellets consisting of MOF-5 with 5 and 10 wt.% ENG additions, have been measured at ambient (296 K) and liquid nitrogen (77 K) temperatures. The experimental data suggest that the H₂ transport in densified MOF-5 is strongly related to the MOF-5 pellet density ρ.     

Investigation of cryo-adsorption hydrogen storage capacity of rapidly synthesized MOF-5 by mechanochemical method

Comparisons were made between the samples mechanochemically (MOF-5(M)) and solvothermally (MOF-5(S)) prepared for the development of efficient hydrogen storage medium. Synthesized samples were undergone structural characterization as well as adsorption equilibrium measurements of hydrogen at temperature-pressure range 77 K–87 K and 0.1–10 MPa. Grand Canonical Monte Carlo (GCMC) simulations were further conducted to study the behaviors of hydrogen molecules adsorbed on MOF-5. It shows that, besides the advantage of large scale synthesis and a lower cost, mechanochemical method respectively brings about 207% and 90.5% increments in the specific surface area and the maximum excess adsorption capacity of hydrogen at 77 K within pressure range 0–10 MPa. Results also reveal that the crystal within MOF-5(M) is regular and distributing uniformly with a mean size only one tenth of that of the MOF-5(S); at 77 K within pressure range 0–10 MPa, Toth equation can predict the adsorption equilibrium data of hydrogen on two MOF-5 samples with a mean relative error less than 1.5%. It suggests that MOF-5(M) is more promising for hydrogen storage by adsorption for practical applications.     

Efficient synthesis for large-scale production and characterization for hydrogen storage of ligand exchanged MOF-74/174/184-M (M = Mg2+, Ni2+)

A semitechnical route (optimized by BASF SE) to synthesize MOF-74/174-M (M = Mg²⁺, Ni²⁺) efficiently in ton-scale production is presented with the goal of mobile and stationary gas storage applications especially for hydrogen as future energy carrier. In addition, a new member of these series of materials, MOF-184-M (M = Mg²⁺, Ni²⁺) is introduced using ligand exchange strategy in order to produce a more porous analogue (possessing large aperture) without loss of crystallinity. This family comprising MOF-74/174/184 are characterized systematically for hydrogen adsorption properties by volumetric measurements with a Sieverts’ apparatus. Replacing the linker by a longer one results in an increase of the BET area from 984 to 3154 m²/g and an enhancement of the excess cryogenic (77 K) hydrogen storage capacity from 1.8 to 4.7 wt%. The heat of adsorption of linker exchanged MOF-174/184 (as a function of uptake) shows similar values to the parent MOF-74, indicating successful construction of expanded MOFs in large scale production. Finally, a usable capacity of these MOFs is investigated for mobile application, revealing that the increasing surface area without strong binding metal sites through longer linker exchange is one of important parameters for improving usable capacity.     

Solvothermal synthesis,nanostructural characterization and gas cryo-adsorption studies in a metal–organic framework (IRMOF-1) material

A nanoporous metal–organic framework material, exhibiting an IRMOF-1 type crystalline structure, was prepared by following a direct solvothermal synthesis approach, using zinc nitrate and terephthalic acid as precursors and dimethylformamide as solvent, combined with supercritical CO₂ activation and vacuum outgassing procedures. A series of advanced characterization methods were employed, including scanning electron microscopy, Fourier-transform infrared radiation spectroscopy and X-ray diffraction, in order to study the morphology, surface chemistry and structure of the IRMOF-1 material directly upon its synthesis. Porosity properties, such as Brunauer–Emmet–Teller (BET) specific area (～520 m²/g) and micropore volume (～0.2 cm³/g), were calculated for the activated sample based on N₂ gas sorption data collected at 77 K. The H₂ storage performance was preliminary assessed by low-pressure (0–1 bar) H₂ gas adsorption and desorption measurements at 77 K. The activated IRMOF-1 material of this study demonstrated a fully reversible H₂ sorption behavior combined with an adequate gravimetric H₂ uptake relative to its BET specific area, thus achieving a value of ～1 wt.% under close-to-atmospheric pressure conditions.     

Synthesis,characterization and hydrogen adsorption properties of metal–organic framework Al-TCBPB

In this work, a new metal–organic framework (MOF) was synthesized by using a large organic ligand 1,3,5-tris[4′-carboxy(1,1′-biphenyl)-4-yl] benzene (abbreviated as TCBPB) and aluminum as the metal that forms the secondary building unit (SBU) by solvothermal method. The MOF, named as Al-TCBPB, was characterized with pore textural properties, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Raman and FT-IR spectroscopy. Hydrogen adsorption was measured volumetrically at ambient pressure and temperatures of 77, 88 and 298 K and at high pressure (up to 9 MPa) for temperatures 77 and 298 K. Pore textural properties revealed a high BET surface area of 2311 m²/g, narrow bimodal pore widths of 11.8 Å and 20 Å and a total pore volume of 0.80 cm³/g. PXRD identified the crystal structure as monoclinic with space group c2/m. This MOF adsorbs 1.53 and 0.83 wt.% of hydrogen at 77 and 88 K, respectively, and pressures up to ambient conditions. At higher pressure of 9 MPa, it demonstrated an excess adsorption of 4.8 and 1.4 wt.% at 77 and 298 K, respectively; these high-pressure data fit well with modified Dubinin–Astakov (D–A) analytical model. The heat of adsorption values of Al-TCBPB vary between 5.9 and 4.9 kJ/mol for the hydrogen adsorption loading of 0.1–0.8 wt.% and decreases monotonically to approximately 2 kJ/mol when the adsorption loading becomes 4.8 wt%.     

Improvement on hydrogen storage thermodynamics and kinetics of the as-milled SmMg11Ni alloy by adding MoS2

In this experiment, the Mg-based hydrogen storage alloys SmMg₁₁Ni and SmMg₁₁Ni + 5 wt.% MoS₂ (named SmMg₁₁Ni-5MoS₂) were prepared by mechanical milling. By comparing the structures and hydrogen storage properties of the two alloys, it could be found that the addition of MoS₂ has brought on a slight change in hydrogen storage thermodynamics, an obvious decrease in hydrogen absorption capacity, an obvious catalytic action on hydrogen desorption reaction, and a lowered onset desorption temperature from 557 to 545 K. Additionally, the addition of MoS₂ could dramatically improve the alloy in its hydrogen absorption and desorption kinetics. To be specific, the hydrogen desorption times of 3 wt.% H₂ at 593, 613, 633 and 653 K were measured to be 1488, 683, 390 and 192 s respectively for the SmMg₁₁Ni alloy, which were reduced to 938, 586, 296 and 140 s for the MoS₂ catalyzed SmMg₁₁Ni alloy at identical conditions. The activation energies of the alloys with and without MoS₂ for hydrogen desorption are 87.89 and 100.31 kJ/mol, respectively. The 12.42 kJ/mol decrease is responsible for the ameliorated hydrogen desorption kinetics by adding catalyst MoS₂.     

Rb and Cs doping effects in sodium borohydride: Density functional theory for hydrogen (H2) storage purpose

Fuel cell technology based on stationary and mobile applications is needing new hydrogen storage materials equipped with huge gravimetric and volumetric hydrogen densities. Examining the fundamental properties of hydrides is an important part of such process, mainly to understand the structure change's impact on the hydrogen storage. Herein, we applied ab-initio density functional theory using full potential linear augmented plane method to explore the effect of rubidium and cesium doping in sodium borohydride, NaBH₄. The electronic structure calculations exposed the semiconducting nature of NaBH₄ and derived doped structures NaRbBH₄ and NaCsBH₄. The hydrogen (H₂) storage capacity is found 10.66 wt %, 3.27 wt % and 2.36 wt % within a reasonable free energy of ?28.514 kJ/mol, ?29.709 kJ, ?28.51 kJ/mol for NaBH₄, NaRbBH₄ and NaCsBH₄ respectively from quasi-harmonic approximation. Also, we extracted the heat capacity and Debye temperature from vibrational analysis based on phonon calculation. The discovered features show the potential use of presented sodium borohydrides for practical H₂ storage devices.     

Hydrogen storage in 1D nanotube-like channels metal–organic frameworks: Effects of free volume and heat of adsorption on hydrogen uptake

Metal–organic Frameworks generate significant interest for their potential application as Hydrogen storage materials. Grand Canonical Monte Carlo (GCMC) simulations were performed at two different temperatures 77 and 300 K over a wide range of pressures to describe H₂ adsorption in 7 metal–organic frameworks (MOFs), which all have the same framework topology but different surface chemistry and different pore sizes. DREIDING and UFF force fields were identified to be able to predict adsorption isotherms for H₂ in MOFs in a reasonable agreement with the experimental data from the literature. This work reveals that at 77 K the total amount of H₂ adsorbed correlates mainly with: the heat of adsorption at low pressure and the free volume at high pressure. While at 300 K the amount adsorbed mainly correlates with the available free volume at both low and high pressure. None of the MOFs studied fulfils DOE requirement, this is due to their low heat of adsorption. The required adsorption energy to meet the DOE targets is estimated to be 34 kJ/mol.     

Increased volumetric hydrogen uptake of MOF-5 by powder densification

The metal-organic framework MOF-5 has attracted significant attention due to its ability to store large quantities of H₂ by mass, up to 10 wt.% absolute at 70 bar and 77 K. On the other hand, since MOF-5 is typically obtained as a bulk powder, it exhibits a low volumetric density and poor thermal conductivity—both of which are undesirable characteristics for a hydrogen storage material. Here we explore the extent to which powder densification can overcome these deficiencies, as well as characterize the impact of densification on crystallinity, pore volume, surface area, and crush strength. MOF-5 powder was processed into cylindrical tablets with densities up to 1.6 g/cm³ by mechanical compaction. We find that optimal hydrogen storage properties are achieved for ρ ∼ 0.5 g/cm³, yielding a 350% increase in volumetric H₂ density with only a modest 15% reduction in gravimetric H₂ excess in comparison to the powder. Higher densities result in larger reductions in gravimetric excess. Total pore volume and surface area decrease commensurately with the gravimetric capacity, and are linked to an incipient amorphization transformation. Nevertheless, a large fraction of MOF-5 crystallinity remains intact in densities up to 0.75 g/cm³, as confirmed from powder XRD. Predictably, the radial crush strength of the pellets is enhanced by densification, increasing by a factor of 4.3 between a density of 0.4 g/cm³ and 0.6 g/cm³. Thermal conductivity increases slightly with tablet density, but remains below the single crystal value.     

A novel hydrogen storage medium of Ca-coated B40: First principles study

Using first principles study, we have investigated the hydrogen storage capacity of Ca-coated B₄₀. Our result shows that Ca prefers to adsorb on the top hollow center of heptagonal ring of B₄₀ due to the large binding energy of ?2.820 eV. Bader charges calculation indicates that charges transfer from Ca to B₄₀ result in an induced electric field so that H₂ molecules are polarized and adsorbed onto the surface of B₄₀ without dissociation. The Ca₆B₄₀ complex can adsorb up to 30 H₂ molecules with average adsorption energy of ?0.177 eV/H₂ and the hydrogen storage gravimetric density reaches up to 8.11 wt.%, higher than the goal from DOE by the year 2020. These findings will suggest a new and potential structure for hydrogen storage in the future.     

Hydrogen storage performance in palladium-doped graphene/carbon composites

In this study a two-dimensional graphene sheet (GS) doped with palladium (Pd) nanoparticles was physically mixed with a superactivated carbon (AC) receptor and used as a hydrogen adsorbent. The hydrogen adsorption/desorption isotherm of the Pd-doped GS catalyst/AC composite (Pd-GS/AC) is determined using a static volumetric measurement at room temperature (RT) and pressure up to 8 MPa. The experiments show that the H₂ uptake capacity of 0.82wt.% for Pd-GS/AC is obviously enhanced, measuring 49% more than the 0.55wt.% for Pd-free GS/AC at RT and 8 MPa. Highly reversible behavior of Pd-GS/AC is also observed. Moreover, the isosteric heat of adsorption for Pd-GS/AC (−14 to −10 kJ/mol) is higher than that for pristine AC (−8 kJ/mol). An increase in H₂ uptake in the Pd-GS/AC suggests the occurrence of a relatively strong interaction between the spilt-over H and the receptor sites due to the spillover effect.     

MOF-5 and activated carbons as adsorbents for gas storage

This paper reports comparatively the capacities of two activated carbons (ACs) and MOF-5 for storing gases. It analyzes, using similar equipments and experimental procedures, the density used to convert gravimetric data to volumetric ones, measuring the density (tap and packing at different pressures). It presents data on porosity, surface area and gas storage (H₂, CH₄ and CO₂) obtained under different temperatures (77 K and RT) and pressures (0.1, 4 and 20 MPa). MOF-5 presents lower volume of narrow micropores than both ACs, making its storage at RT lower, independently of the gas used (H₂, CH₄ and CO₂) and the basis of reporting data (gravimetric or volumetric). For H₂ at 77 K the reliability of the results depends too much on the density used. It is shown that the outstanding volumetric performance of MOF-5, in relation to ACs, is due to the use of an unrealistic high density (crystal density) that, not including the adsorbent inter-particle space, gives an apparently high volumetric gas storage capacity. When a density measured similarly in both types of adsorbents is used (e.g. tap or packing densities) MOF-5 presents, for all gases and conditions studied, lower adsorption capacities on volumetric basis and storage capacities than ACs.     

Density functional studies on the hydrogen storage capacity of boranes and alanes based cages

The hydrogen storage (H-storage) capacity of various boranes and alanes have been investigated using density functional theory (DFT) based M05-2X method employing 6–31+G** basis set. The changes in the H-storage capacities of borane and alane upon substitution of antipodal atoms in the cages by C, Si, and N have also been investigated. It is found from the calculations that a maximum of 20 H₂ molecules can be adsorbed on the deltahedron faces of these cages. The maximum gravimetric density has been observed for boranes when compared to alanes. The H-storage capacity of closo-borane dianion [B₁₂H₁₂]²⁻, monocarborane [CB₁₁H₁₂]¹⁻, dicarborane [C₂B₁₀H₁₂], and closo-azaborane [NB₁₁H₁₂] cages is almost similar (∼22 wt.%). Among these cages, B_BB dianion show higher binding energy (BE) and BE per H₂ molecule (BE/nH₂) which are 181.06 and 9.03 kJ/mol, respectively. In the case of alanes, dicarbalane [C₂Al₁₀H₁₂] has maximum H-storage capacity of 11.6 wt.%. Based on these findings, a new MOF with carborane (MOF-5_CC) as linker has been designed. The calculation on the new MOF-5B_CC reveals that it has H-storage capacity of 6.4 wt.% with BE/nH₂ of 3.02 kJ/mol.     

Fullerene-impregnated IRMOFs for balanced gravimetric and volumetric H2 densities: A combined DFT and GCMC simulations study

This paper aimed to study the effects of fullerene (C₆₀) impregnation on the isoreticular metal-organic framework (IRMOF) materials MOF-650 (ZnO₄ nodes were connected to azulenedicarboxylate linkers), MOF-5(ZnO₄ nodes were connected to benzenedicarboxylate linkers), and IRMOF-10 (ZnO₄ nodes were connected to biphenyldicarboxylate linkers) for H₂ storage, these IRMOFs had similar structures but different pore volumes and organic linkers. Density functional theory (DFT) and grand canonical monte Carlo (GCMC) calculations indicated that C₆₀ plays an important role in balancing the gravimetric and volumetric H₂ densities of the IRMOFs. The C₆₀@IRMOFs revealed improved volumetric density when H₂ was undersaturated but reduced gravimetric density under H₂ saturation. The saturated gravimetric H₂ density of the IRMOFs was decided by the free volume. At 77 K, C₆₀@MOF-650 had a gravimetric H₂ density of 5.3 wt% and volumetric H₂ density of 42 g/L under 10 bar, and C₆₀@IRMOF-10 had a gravimetric H₂ density of 7.4 wt% and volumetric H₂ density of 43 g/L under 18 bar. These values nearly meet the United States Department of Energy (DOE) gravimetric and volumetric H₂ density ultimate targets (gravimetric H₂ density, 6.5 wt%; volumetric H₂ density, 50  g/L) under ambient pressures. Among the studied IRMOFs, C₆₀@MOF-650 and C₆₀@IRMOF-10 demonstrated the best H₂ storage properties at 233 and 298 K.     

Synthesis and hydrogen-storage performance of interpenetrated MOF-5/MWCNTs hybrid composite with high mesoporosity

Metal-organic frameworks (MOFs) exhibiting high surface area and tunable pore size own broad application prospects. Compared with existing MOFs, MOF-5 [Zn₄O(bdc)₃] is a promising hydrogen storage material due to high H₂ uptake capacity and thermostability. However, further wider applications of MOF-5 have been limited because atmospheric moisture levels cause MOF-5 instability. MOF-5 and multi-walled carbon nanotubes (MWCNTs) hybrid composite (denoted MOFMC) can enhance stability toward ambient moisture and improve hydrogen storage capacity. In this paper, the MOFMC, which has an interpenetrated structure with high mesoporosity, was synthesized. The MOFMC is denoted as Int-MOFMC-meso. It stored 2.02 wt% H₂ at 77 K under 1 bar, which is higher than the MOF-5 with similar structure and the earlier reported MOFMC material. Moreover, the Int-MOFMC-meso can also show more excellent performance of thermostability and moisture stability than the MOF-5 with similar structure.